Process for the preparation of triazolinone herbicides

ABSTRACT

A process for the preparation of substituted 1,2,4-triazoline-3(2H)-ones of general formula (I) ##STR1## by reacting an amide of general formula (IV) ##STR2## with phosgen or thiophosgen or a phosgen substitute or thiophosgen substitute to a compound of general formula V ##STR3## and subsequent reaction of (V) with a compound of general formula (VI) or of an acid addition salt of (VI) 
     
         Q--NH--NH--CO--R.sup.26                                    (VI) 
    
     to compounds of general formula (I). 
     Compounds of general formula (I) can be used as herbicides.

BACKGROUND OF THE INVENTION

1. Field of Invention

The invention relates to a novel process for the preparation of1,2,4-triazoline-3(2H)-ones, hereinafter also referred to in simplifiedform as triazolinones, a class of compound of general formula (I),##STR4## where

X=O or S,

R¹ =(C₂ -C₈) alkoxyalkyl, (C₂ -C₈) haloalkoxyalkyl, (C₁ -C₈) alkyl, (C₁-C₈) haloalkyl, (C₁ -C₈) cyanoalkyl, (C₂ -C₈) alkylthioalkyl, (C₂ -C₈)alkylsulfinylalkyl, (C₂ -C₈) alkylsulfonylalkyl, (C₇ -C₈) arylalkyl forexample benzyl, (C₂ -C₈) alkenyl, (C₂ -C₈) haloalkenyl, (C₂ -C₈)alkinyl, (C₂ -C₈) haloalkinyl, aryl for example naphthyl or phenyl, thatmay be substituted once or many times with halogen, (C₁ -C₃) alkyl or(C₁ -C₃) alkoxy, heteroaryl for example pyridine, where heteroaryl mayoptionally be substituted by halogen,

R² and R³, independently of one another represent, H, (C₂ -C₆)alkoxyalkyl, (C₂ -C₆) haloalkoxyalkyl, (C₁ -C₆) alkyl, (C₁ -C₆)haloalkyl, (C₁ -C₆) cyanoalkyl, (C₁ -C₆) alkylthio, (C₂ -C₆)alkylthioalkyl, (C₂ -C₆) alkylsulfinylalkyl, (C₂ -C₆)alkylsulfonylalkyl, (C₇ -C₈) arylalkyl for example benzyl, (C₂ -C₆)alkenyl, (C₂ -C₆) haloalkenyl, (C₂ -C₆) alkinyl, (C₂ -C₆) haloalkinyl;aryl for example naphthyl or phenyl, that may be substituted once ormany times with halogen, (C₁ -C₃) alkyl or (C₁ -C₃) alkoxy, heteroarylfor example pyridine, where

R¹ and R² may also be associated to form a ring to produce structure(II), ##STR5## where

n and m independently of one another are 0, 1, 2 or 3,

Z=CR⁴ R⁵, O, S, S(O), S(O)₂, N((C₁ -C₄)alkyl), N((C₁ -C₄)haloalkyl),C═O, C═N--R⁴ or C═S,

R⁴ =H, (C₁ -C₃) alkyl, halogen, (C₁ -C₆) alkoxy, (C₁ -C₆) haloalkyl, (C₁-C₆) haloalkoxy, (C₂ -C₆) alkylcarbonyloxy or (C₂ -C₆)haloalkylcarbonyloxy,

R⁵ =H, (C₁ -C₃) alkyl or halogen, where R⁴ and R⁵, independently of oneanother, can substitute the ring once or many times and occupy up to 12(m=3, n=3) positions,

Q stands for one of the radicals ##STR6## where

W=O or S,

R⁶ =H, halogen,

R⁷ =H, (C₁ -C₈) alkyl, (C₁ -C₈) haloalkyl, halogen, OH, OR¹², SH,S(O)_(p) R¹², COR¹², CO₂ R¹², C(O)SR¹², C(O)NR¹⁴ R¹⁵, CHO, CR¹⁴ =NOR²¹,CHCR²² CO₂ R¹², CH₂ CHR²² CO₂ R¹², CO₂ N═CR¹⁶ R¹⁷, NO₂, CN, NHSO₂ R¹⁸,NHSO₂ NHR¹⁸, NR¹² R²³, NH₂ or phenyl, optionally substituted by R²⁴,

p=0,1 or 2, R⁸ =(C₁ -C₂) alkyl, (C₁ -C₂) haloalkyl, OCH₃, SCH₃, OCHF₂,halogen, CN or NO₂,

R⁹ =H, (Cl-C₃) alkyl or halogen,

R¹⁰ =H, (C₁ -C₃) alkyl, halogen, (C₁ -C₃) haloalkyl, cyclopropyl, Vinyl,C₂ -C₈ -alkinyl, CN, C(O)R²³,CO₂ R²³, C(O)NR²³ R²⁵, CR¹⁹ R²⁰ CN, CR¹⁹R²⁰ C(O)R²³, CR¹⁹ R²⁰ CO₂ R²³, CR¹⁹ R²⁰ C(O)NR²³ R²⁵, CHR¹⁹ OH, CHR¹⁹OC(O)R²³ or OCHR¹⁹ OC(O)NR²³ R²⁵, or, when Q equals Q-2, R⁹ and R¹⁰ cantogether with the carbon atom to which they are bound be C═O,

R¹¹ =H, (C₁ -C₆) alkyl, (C₁ -C₆) haloalkyl, (C₃ -C₆) haloalkenyl, (C₂-C₆) alkoxyalkyl, (C₃ -C₆) alkenyl, (C₃ -C₆) alkinyl, (C₃ -C₆)haloalkinyl, (C₄ -C₇) cycloalkylalkyl, ##STR7##

R¹² =(C₁ -C₈) alkyl, (C₃ -C₈) cycloalkyl, (C₃ -C₈) alkenyl, (C₃ -C₈)alkinyl, (C₁ -C₈) haloalkyl, (C₂ -C₈) alkoxyalkyl, (C₂ -C₈)alkylthioalkyl, (C₂ -C₈) alkylsulfinylalkyl, (C₂ -C₈)alkylsulfonylalkyl, (C₄ -C₈) alkoxyalkoxyalkyl, (C₄ -C₈)cycloalkylalkyl, (C₆ -C₈) cycloalkoxyalkyl, (C₄ -C₈) alkenyloxyalkyl,(C₄ -C₈) alkinyloxyalkyl, (C₃ -C₈) haloalkoxyalkyl, (C₄ -C₈)haloalkenyloxyalkyl, (C₄ -C₈) haloalkinyloxyalkyl, (C₆ -C₈)cycloalkylthioalkyl, (C₄ -C₈) alkenylthioalkyl, (C₄ -C₈)alkinylthioalkyl, (C₁ -C₄) alkyl, substituted by phenoxy or benzyloxy,each ring optionally substituted by halogen, (C₁ -C₃) alkyl or (C₁ -C₃)haloalkyl, (C₄ -C₈) trialkylsilylalkyl, (C₃ -C₈) cyanoalkyl, (C₃ -C₈)halocycloalkyl, (C₃ -C₈) haloalkenyl, (C₅ -C₈) alkoxyalkenyl, (C₅ -C₈)haloalkoxyalkenyl, (C₅ -C₈) alkylthioalkenyl, (C₃ -C₈) haloalkinyl, (C₅-C₈) alkoxyalkinyl, (C₅ -C₈) haloalkoxyalkinyl, (C₅ -C₈)alkylthioalkinyl, (C₂ -C₈) alkylcarbonyl, benzyl, optionally substitutedby halogen, (C₁ -C₃) alkyl or (C₁ -C₃) haloalkyl, CHR¹⁹ COR¹³, CHR¹⁹P(O)(OR¹³) CHR¹⁹ P(S) (OR¹³)₂, P(O) (OR¹³)₂, P(S)(OR¹³)₂, CHR¹⁹ C(O)NR¹⁴R¹⁵, CHR¹⁹ C(O)NH₂, CHR¹⁹ CO₂ R¹³, CO₂ R¹³, SO₂ R¹³, phenyl, optionallysubstituted by R²⁴, ##STR8##

R¹³ =(C₁ -C₆) alkyl, (C₁ -C₆) haloalkyl, (C₃ -C₆) alkenyl or (C₃ -C₆)alkinyl,

R¹⁴ and R¹⁶ =independently of one another, H or (C₁ -C₄) alkyl,

R¹⁵ and R¹⁷ =independently of one another, (C₁ -C₄) alkyl or phenyl,optionally substituted by halogen, (C₁ -C₃) alkyl or (C₁ -C₃) haloalkyl,or

R¹⁴ and R¹⁵ can, together with the nitrogen atom that binds them, form apiperidinyl-, pyrrolidinyl- or morpholinyl-ring, each ring optionallysubstituted by (C₁ -C₃) alkyl, phenyl or benzyl, or

R¹⁶ and R¹⁷ can, together with the carbon atom that binds them, be (C₃-C₈) cycloalkyl,

R¹⁸ =(C₁ -C₄) alkyl or (C₁ -C₄) haloalkyl,

R¹⁹ and R²⁰ =independently H or (C₁ -C₅) alkyl,

R²¹ H, (C₁ -C₆) alkyl, (C₃ -C₆) alkenyl or (C₃ -C₆) alkinyl,

R²² and R²⁷ =independently of one another, H, (C₁ -C₄) alkyl or halogen,or

R¹² and R²² can together form a (C₂ -C₃) alkylen,

R²³, R²⁴ and R²⁸ =independently of one another, H or (C₁ -C₄) alkyl,

R²⁵ =(C₁ -C₂) alkyl, (C₁ -C₂) haloalkyl, OCH₃, SCH₃, OCHF₂, halogen, CNor NO₂ and

R²⁶ =H, (C₁ -C₅) alkyl, (C₁ -C₅) haloalkyl, (C₃ -C₆) cycloalkyl, (C₃-C₆) halocycloalkyl, (C₁ -C₅) alkoxy, (C₁ -C₅) haloalkoxy and phenyl,that may optionally be substituted up to three times optionally byhalogen, NO₂, cyano, (C₁ -C₂) alkyl, (C₁ -C₂) haloalkyl, (C₁ -C₂) alkoxyor (C₁ -C₂) haloalkoxy,

R²⁹ =H, halogen or (C₁ -C₆) alkyl,

R³⁰ =H, (C₁ -C₄) alkyl or halogen.

The compounds of formulae I or II are highly active herbicides, whichact as protoporphyrinogen oxidase inhibitor and control unwanted grassesand weeds, even when used in small amounts. I and II are, for example,of great interest for cultures with plantations where fast-growing androbust destructive plants impair the harvest. Thanks to the excellentselectivity of type I or II, these compounds can, however, also be usedin cultivated plants, for example maize, soya, wheat or barley to combatdestructive plants.

2. Related Art

Known processes for the preparation of compound I generally start withan appropriately substituted phenylhydrazine which is converted into thecorresponding triazolidinone by reaction with an N-(1-alkoxy)alkylidenealkylcarbamate or with an α-ketocarboxylic acid derivative and bysubsequent Schmidt rearrangement into the corresponding triazolidinones.

EP 0 220 952 for example describes the conversion carried out in xyleneof 2-chlorophenyl hydrazine with N-(1-ethoxy)ethylidene ethylcarbamateinto triazolinone unsubstituted in 4-position which is then alkylated inan independent reaction step in dimethylformamide into thetri-substituted triazolinone. It is very laborious to prepare bicyclictriazolinones in this manner.

U.S. Pat. No. 4,818,275 and U.S. Pat. No. 4,818,276 also describeprocesses for substituted triazolinones. Acid condensation of the phenylhydrazine used with an a-ketocarboxylic acid first yields the hydrazonewhich undergoes Schmidt rearrangement by reaction with diphenylphosphorylazide and is hereby converted into triazolinone. Thetriazolinone formed also has to be alkylated into the final compound ina subsequent reaction step. It is also very laborious to synthesisebicyclic triazolinones in this manner and the azide used causes problemsof technical safety when the compounds are synthesised on an industrialscale.

In other known processes for the preparation of individualrepresentatives of compound type II the reaction generally occurs viathe corresponding amidrazone which is reacted to bicyclic compounds.##STR9## DE 28 01 429 describes a process for the preparation ofcompounds of type II in which it is necessary to react 2-piperidone,that first has to be suitably activated using methods known from theliterature (see Houben-Weyl, "Methoden der organischen Chemie", Vol.11/2, p. 578; and DE-OS 19 12 739 and DE-OS 19 12 737) with the HCl-saltof the correspondingly substituted phenylhydrazine to amidrazone (III)(see DT-OS 22 35 177) and cyclisises the amidrazone formed withchloroformic acid methyl ester or phosgen into THF with addition of baseto compounds of type II.

In another process (see PCT/WO 94/22828)N-carboxymethyl-2-iminopiperidine hydrochloride is described asactivated intermediate compound. The hydrolysis-sensitive intermediatecompound is coupled with the correspondingly substituted phenylhydrazineand then cyclisised by acid catalysis to form triazolinone.

The process according to EP 0 317 947 A2 for the synthesis oftriazolinones includes the reaction of N-carboxyalkyl lactams with aphenylhydrazine to amidrazone by boiling under reflux in xylene. Thebicyclic triazolinone is formed by reaction with phosgen. A disadvantageof the process is that the condensation step to amidrazone only producesa yield of 21 % in the presence of P₄ O₁₀ as dessicating agent.

The known processes have the disadvantages that they can, in part, onlybe realised via long synthesis routes which in part lead viaintermediate steps that are laborious to produce and to treat, that theysupply moderate yields and in part use costly and not always innocuousstarting substances and that various by-products are formed whichnecessitate laborious purification steps.

SUMMARY OF THE INVENTION

It is therefore an object of the invention to provide a process which isdevoid of the above disadvantages and which is economically moreinteresting.

This object for the preparation of compounds of type (I), ##STR10##where

X=O or S,

R¹ =(C₂ -C₈) alkoxyalkyl, (C₂ -C₈) haloalkoxyalkyl, (C₁ -C₈) alkyl, (C₁-C₈) haloalkyl, (C₁ -C₈) cyanoalkyl, (C₂ -C₈) alkylthioalkyl, (C₂ -C₈)alkylsulfinylalkyl, (C₂ -C₈) alkylsulfonylalkyl, (C₇ -C₈) arylalkyl forexample benzyl, (C₂ -C₈) alkenyl, (C₂ -C₈) haloalkenyl, (C₂ -C₈)alkinyl, (C₂ -C₈) haloalkinyl, aryl for example naphthyl or phenyl, thatmay be substituted once or many times with halogen, (C₁ -C₃) alkyl or(C₁ -C₃) alkoxy, heteroaryl for example pyridine, where heteroaryl mayoptionally be substituted by halogen,

R² and R³, independently of one another represent, H, (C₂ -C₆)alkoxyalkyl, (C₂ -C₆) haloalkoxyalkyl, (C₁ -C₆) alkyl, (C₁ -C₆)haloalkyl, (C₁ -C₆) cyanoalkyl, (C₁ -C₆) alkylthio, (C₂ -C₆)alkylthioalkyl, (C₂ -C₆) alkylsulfinylalkyl, (C₂ -C₆)alkylsulfonylalkyl, (C₇ -C₈) arylalkyl for example benzyl, (C₂ -C₆)alkenyl, (C₂ -C₆) haloalkenyl, (C₂ -C₆) alkinyl, (C₂ -C₆) haloalkinyl,aryl for example naphthyl or phenyl, that may be substituted once ormany times with halogen, (C₁ -C₃) alkyl or (C₁ -C₃) alkoxy, heteroarylfor example pyridine, where

R¹ and R² may also be associated to form a ring to produce structure(II), ##STR11## where

n and m independently of one another are 0, 1, 2 or 3,

Z=CR⁴ R⁵, O, S, S(O), S(O)₂, N((C₁ -C₄)alkyl), N((C₁ -C₄)haloalkyl),C═O, C═N--R⁴ or C═S,

R⁴ =H, (C₁ -C₃) alkyl, halogen, (C₁ -C₆) alkoxy, (C₁ -C₆) haloalkyl, (C₁-C₆) haloalkoxy, (C₂ -C₆) alkylcarbonyloxy or (C₂ -C₆)haloalkylcarbonyloxy,

R⁵ =H, (C₁ -C₃) alkyl or halogen, where R⁴ and R⁵, independently of oneanother, can substitute the ring once or many times and occupy up to 12(m=3, n=3) positions,

Q stands for one of the radicals ##STR12## where

W=O or S,

R=H, halogen,

R=H, (C₁ -C₈) alkyl, (C₁ -C₈) haloalkyl, halogen, OH, OR¹², SH, S(O)_(p)R¹², COR¹², CO₂ R¹², C(O)SR¹², C(O)NR¹⁴ R¹⁵, CHO, CR¹⁴ ═NOR²¹, CHCR²²CO₂ R¹², CH₂ CHR²² CO₂ R¹², CO₂ N═CR¹⁶ R¹⁷, NO₂, CN, NHSO₂ R¹⁸, NHSO₂NHR¹⁸, NR¹² R²³, NH₂ or phenyl, optionally substituted by R²⁴,

p=0,1 or 2,

R⁸ =(C₁ -C₂) alkyl, (C₁ -C₂) haloalkyl, OCH₃, SCH₃, OCHF₂, halogen, CNor NO₂,

R⁹ =H, (C₁ -C₃) alkyl or halogen,

R¹⁰ =H, (C₁ -C₃) alkyl, halogen, (C₁ -C₃) haloalkyl, cyclopropyl, Vinyl,C₂ -alkinyl, CN, C(O)R²³, CO₂ R²³, C(O)NR²³ R²⁵, CR¹⁹ R²⁰ CN, CR¹⁹ R²⁰C(O)R²³, CR¹⁹ R²⁰ CO₂ R²³, CR¹⁹ R²⁰ C(O)NR²³ R²⁵, CHR¹⁹ OH, CHR¹⁹OC(O)R²³ or OCHR¹⁹ OC(O)NR²³ R²⁵, or, when Q equals Q-2, R⁹ and R¹⁰ cantogether with the carbon atom to which they are bound be C═O,

R¹¹ =H, (C₁ -C₆) alkyl, (C₁ -C₆) haloalkyl, (C₃ -C₆) haloalkenyl, (C₂-C₆) alkoxyalkyl, (C₃ -C₆) alkenyl, (C₃ -C₆) alkinyl, (C₃ -C₆)haloalkinyl, (C₄ -C₇) cycloalkylalkyl, ##STR13##

R¹² =(C₁ -C₈) alkyl, (C₃ -C₈) cycloalkyl, (C₃ -C₈) alkenyl, (C₃ -C₈)alkinyl, (C₁ -C₈) haloalkyl, (C₂ -C₈) alkoxyalkyl, (C₂ -C₈)alkylthioalkyl, (C₂ -C₈) alkylsulfinylalkyl, (C₂ -C₈)alkylsulfonylalkyl, (C₄ -C₈) alkoxyalkoxyalkyl, (C₄ -C₈)cycloalkylalkyl, (C₆ -C₈) cycloalkoxyalkyl, (C₄ -C₈) alkenyloxyalkyl,(C₄ -C₈) alkinyloxyalkyl, (C₃ -C₈) haloalkoxyalkyl, (C₄ -C₈)haloalkenyloxyalkyl, (C₄ -C₈) haloalkinyloxyalkyl, (C₆ -C₈)cycloalkylthioalkyl, (C₄ -C₈) alkenylthioalkyl, (C₄ -C₈)alkinylthioalkyl, (C₁ -C₄) alkyl, substituted by phenoxy or benzyloxy,each ring optionally substituted by halogen, (C₁ -C₃) alkyl or (C₁ -C₃)haloalkyl, (C₄ -C₈) trialkylsilylalkyl, (C₃ -C₈) cyanoalkyl, (C₃ -C₈)halocycloalkyl, (C₃ -C₈) haloalkenyl, (C₅ -C₈) alkoxyalkenyl, (C₅ -C₈)haloalkoxyalkenyl, (C₅ -C₈) alkylthioalkenyl, (C₃ -C₈) haloalkinyl, (C₅-C₈) alkoxyalkinyl, (C₅ -C₈) haloalkoxyalkinyl, (C₅ -C₈)alkylthioalkinyl, (C₂ -C₈) alkylcarbonyl, benzyl, optionally substitutedby halogen, (C₁ -C₃) alkyl or (C₁ -C₃) haloalkyl, CHR¹⁹ COR¹³, CHR¹⁹P(O)(OR¹³)₂ CHR¹⁹ P(S) (OR¹³)₂, P(O) (OR¹³)₂, P(S)(OR¹³)₂, CHR¹⁹C(O)NR¹⁴ R¹⁵, CHR¹⁹ C(O)NH₂, CHR¹⁹ CO₂ R¹³, CO₂ R¹³, SO₂ R¹³, phenyl,optionally substituted by R²⁴, ##STR14##

R¹³ =(C₁ -C₆) alkyl, (C₁ -C₆) haloalkyl, (C₃ -C₆) alkenyl or (C₃ -C₆)alkinyl,

R¹⁴ and R¹⁶ =independently of one another, H or (C₁ -C₄) alkyl,

R¹⁵ and R¹⁷ =independently of one another, (C₁ -C₄) alkyl or phenyl,optionally substituted by halogen, (C₁ -C₃) alkyl or (C₁ -C₃) haloalkyl,or

R¹⁴ and R¹⁵ can, together with the nitrogen atom that binds them, form apiperidinyl-, pyrrolidinyl- or morpholinyl-ring, each ring optionallysubstituted by (C₁ -C₃) alkyl, phenyl or benzyl, or

R¹⁶ and R¹⁷ can, together with the carbon atom that binds them, be (C₃-C₈) cycloalkyl,

R¹⁸ =(C₁ -C₄) alkyl or (C₁ -C₄) haloalkyl,

R¹⁹ and R²⁰ =independently H or (C₁ -C₅) alkyl,

R²¹ =H, (C₁ -C₆) alkyl, (C₃ -C₆) alkenyl or (C₃ -C₆) alkinyl,

R²² and R²⁷ =independently of one another, H, (C₁ -C₄) alkyl or halogen,or

R¹² and R²² can together form a (C₂ -C₃) alkylen,

R²³, R²⁴ and R²⁸ =independently of one another, H or (C₁ -C₄) alkyl,

R²⁵ =(C₁ -C₂) alkyl, (C₁ -C₂) haloalkyl, OCH₃, SCH₃, OCHF₂, halogen, CNor NO₂ and

R²⁶ =H, (C₁ -C₅) alkyl, (C₁ -C₅) haloalkyl, (C₃ -C₆) cycloalkyl, (C₃-C₆) halocycloalkyl, (C₁ -C₅) alkoxy, (C₁ -C₅) haloalkoxy and phenyl,that may optionally be substituted up to three times optionally byhalogen, NO₂, cyano, (C₁ -C₂) alkyl, (C₁ -C₂) haloalkyl, (C₁ -C₂) alkoxyor (C₁ -C₂) haloalkoxy,

R²⁹ =H, halogen or (C₁ -C₆) alkyl,

R³⁰ =H, (C₁ -C₄) alkyl or halogen is solved in the process according tothe invention by reacting amides of general formula (IV) ##STR15## whereR¹, R² and R³ have the meaning given above in a manner known per se withphosgen or thiophosgen or a phosgen substitute or thiophosgen substituteoptionally in a solvent to a compound of formula (V) ##STR16## where R¹,R², R³ and X have the meaning given above and these compounds of formula(V) are subsequently reacted with a compound of formula (VI) or an acidaddition salt thereof,

    Q--NH--NH--CO--R.sup.26                                    (VI)

where Q and R²⁶ have the meaning given above, optionally in the presenceof a diluting agent and optionally in the presence of a base and thenreacts in the presence of an acid and optionally by increasing thetemperature into a compound of formulae (I) or (II).

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

It is preferably possible according to the process of the invention toproduce compounds of type II ##STR17## where

X=0,

n and m independently of one another are 0, 1 or 2,

Z=CR⁴ R⁵, O, S, C═O or C═S,

R⁴ =H, (C₁ -C₂) alkyl, (C₁ -C₂) haloalkyl, fluorine, chlorine, (C₁ -C₃)alkoxy or (C₁ -C₃) haloalkoxy,

R³ and R⁵ can independently of one another be H, (C₁ -C₂) alkyl,fluorine or chlorine,

Q=Q-1, Q-2 or Q-5,

R⁷ H, (C₁ -C₈) alkyl, (C₁ -C₈) haloalkyl, halogen, OH, OR¹², SH,S(O)_(p) R12, COR¹², CO₂ R¹², C(O)SR¹², C(O)NR¹⁴ R¹⁵, CHO, CH═CHCO₂ R¹²,CO₂ N═CR¹⁶ R¹⁷, NO₂, CN, NHSO₂ R¹⁸ or NHSO₂ NHR¹⁵ and

R¹² =(C₁ -C₄) alkyl, (C₃ -C₄) alkenyl, (C₃ -C₄) alkinyl, (C₂ -C₄)alkoxyalkyl, (C₁ -C₄) haloalkyl, (C₃ -C₄) haloalkenyl or (C₃ -C₄)haloalkinyl,

R²⁶ =H, by reacting amides of general formula VII ##STR18## where n, m,Z, R³, R⁴ and R⁵ have the meaning given above in a manner known per sewith phosgen or thiophosgen or a phosgen substitute or thiophosgensubstitute optionally in a solvent to a compound of formula VIII##STR19## where n, m, X, Z, R³, R⁴ and R⁵ have the meaning given aboveand these compounds of formula (VIII) are then reacted with a compoundof formula (VI) or an acid addition salt hereof

    Q--NH--NH--CO--R.sup.26                                    (VI)

where Q and R²⁶ have the meaning given above optionally in the presenceof a diluting agent and optionally first in the presence of a base andthen in the presence of an acid and optionally by increasing thetemperature to a compound of formula (II).

Quite particularly preferred is a process for the preparation ofcompounds of type II ##STR20## where

X=0,

n and m independently of one another are 0, 1 or 2,

Z=CH₂, CHF, CF₂ or CHCl,

R⁴ =H, (C₁ -C₂) alkyl, (C₁ -C₂) haloalkyl, fluorine, chlorine,

R⁵ =H, (C₁ -C₂) alkyl, fluorine, chlorine,

R³ =H,

Q=Q-1 or Q-5,

R⁷ =H, (C₁ -C₈) alkyl, (C₁ -C₈) haloalkyl, halogen, OH, OR¹², SH,S(O)_(p) R¹², COR¹², CO₂ R¹², C(O)SR¹², C(O)NR¹⁴ R¹⁵, CHO, CH═CHCO₂ R¹²,CO₂ N═CR¹⁶ R¹⁷, NO₂, CN, NHSO₂ R¹⁸ or NHSO₂ NHR¹⁵ and

R¹² =(C₁ -C₄) alkyl, (C₃ -C₄) alkenyl, (C₃ -C₄) alkinyl, (C₂ -C₄)alkoxyalkyl, (C₁ -C₄) haloalkyl, (C₃ -C₄) haloalkenyl or (C₃ -C₄)haloalkinyl, and

R⁸ =halogen, CN or NO₂

R²⁶ =H by reacting amides of general formula (VII) ##STR21## where n, m,X, Z, R³, R⁴ and R⁵ have the meaning given above in a manner known perse with phosgen or phosgen substitute to compounds of type (VIII)##STR22## and this compound of type (VIII) is then reacted with acompound of formula (VI) or an acid addition salt thereof

    Q--NH--NH--CO--R.sup.26                                    (VI)

where Q and R²⁶ have the meaning given above optionally in the presenceof a diluting agent and optionally in the presence of a base and thenreacts in the presence of an acid and optionally by increasing thetemperature to a compound of formula (II).

Quite particularly preferred is the process of the invention for thepreparation of the compound (IX) ##STR23## by reacting 2-piperidone withphosgen or a phosgen substitute optionally in a solvent in a mannerknown per se to a compound of formula (X) ##STR24## and then allows thiscompound of formula (X) to react with a compound of formula (XI) or anacid addition salt thereof, ##STR25## optionally in the presence of adiluting agent and optionally in the presence of a base and then in thepresence of an acid and optionally with temperature increase into acompound of formula (IX).

The term "alkyl groups" is understood to mean both "straight-chain" andalso "branched" alkyl groups. The term "straight-chain alkyl group" isunderstood for example to mean radicals such as methyl, ethyl, n-propyl,n-butyl, n-pentyl, n-hexyl, "branched alkyl group" radicals such as forexample isopropyl or tert.-butyl. "Cycloalkyl" is for example understoodto mean radicals such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl or cycloheptyl. The designation halogen stands for fluorine,chlorine, bromine or iodine. The designation "alkoxy group" representsfor example methoxy, ethoxy, propoxy, butoxy, isopropoxy, isobutoxy orpentoxy.

Advantageous variants of the process of the invention are protected inthe claims dependent on claim 1-4.

A preferred embodiment is a synthesis variant in which the compound ofgeneral formula (V) ##STR26## can be obtained in high yield in a mannerknown from the literature according to U.S. Pat. No. 3,080,358 byreacting the amide (IV) ##STR27## with 2-6 mol equivalents of phosgen orthiophosgen or phosgen substitute or thiophosgen substitute in an inertorganic solvent, for example in an aromatic solvent such as toluene,chlorobenzene, a halogenated hydrocarbon such as chloroform, methylenechloride, an ether such as diisopropyl ether, tert. butylmethyl ether,tetrahydrofuran or diethyl ether, acetonitrile or carboxylic acid ester,for example acetic acid ethyl ester, acetic acid methyl ester or aceticacid isopropyl ester, at temperatures between -20° C. to +120° C.,preferably -20° C. to +70° C. Excess phosgen or thiophosgen is drivenout and the solvent optionally drawn off. At 0°-5° C. the compound offormula (V), optionally dissolved in a solvent is added to a solution ofthe compound of formula (VI) or of an acid addition salt of (VI), suchas for example a HCl salt or a H₂ SO₄ salt, in the same solvent or in adifferent, above cited solvent, optionally in the presence of an acidacceptor, for example an organic base such as triethylamine, tetramethylpiperidine, tributylamine or pyridine or an inorganic base, for exampleNaOH, KOH, Ca(OH)₂, CaO, Na₂ CO₃, K₂ CO₃, CaCO₃, NaHCO₃, KHCO₃ oralkoholates for example NaOCH₃ or NaOC₂ H₅, where the compound (XV) isfirst formed, ##STR28## which can then be converted optionally in thepresence of an organic or inorganic acid, such as for example HCl, H₂SO₄ HNO₃, HCO₂ H, p-toluene sulfonic acid, acetic acid, camphorsulfonicacid or H₃ PO₄ or an acid ion exchanger and/or by increasing thetemperature, for example up to the boiling point of the solvent used,into the compounds of formula (I) or (II). The cyclisation of (XV) to(I) or (II) is advantageously carried out with acid catalysis and/ortemperature increase. Secondary reactions may optionally occur withoutintermediate isolation in the same solvent.

During the reaction to compound (XV) 1-4 molar equivalents of base,particularly preferred 1.5-3.5 molar equivalents of base areadvantageously added, where 1 molar equivalent of base serves to releasethe corresponding acylphenyl hydrazine from the optionally usedacylphenyl hydrazine•acid addition salt. Conversion (cyclisation) ofcompound (XV) into (I) necessitates a certain acid excess. It has beenfound that the reaction is accelerated more strongly the greater theacid excess. The amount of acid added depends on the previously usedamount of base. Particularly preferred acids are H₂ SO₄ and HCl. Atemperature increase, advantageously up to the boiling point of thesolvent, accelerates the cyclisation to (I).

In the process according to the invention, the amide unit (IV) is doublyactivated in one step via economically very interesting phosgenation orthiophosgenation with the result that a process technology andeconomically substantially more laborious stepwise activation such asfor example according to EP 0 220 952 can be avoided.

Similarly, in the process according to the invention the reaction to (I)occurs in the desired manner starting from (V) and (VI) in one processstep, with no need for intermediate working up. This means that comparedto known processes, such as for example described in DE 28 01 429, thereis a distinct process technology advantage in that coupling, splittingoff of the protecting group and cyclisation to the compound of formula(I) can be achieved in just one step.

Using the process described, the reaction can occur in a single potprocess and without isolation of intermediate steps, with the resultthat laborious working up techniques are avoided and the process of theinvention permits a smooth course of reaction and by-product formationis extensively avoided and the total yield of (I) is increased.Similarly, the reaction can occur with isolation of the intermediatestep (XV).

Amides of general formulae (IV) and (VII) are commercially obtainable orsynthesisable after Houben-Weyl, "Methoden der Organischen Chemie", E5,"Carbonsauren und carbonsaure-Derivate", part 2, p. 934 ff.

The preparation of compound (XI) occurs by formylation of compounds(XII) or (XIII) ##STR29## by analogy with current processes known fromthe literature (see Houben-Weyl, "Methoden der Organ. Chemie", Vol. 15I,p. 165ff; J. March "Advanced Organic Chemistry", 3rd edition, p.375ff)., where from (XIII) first (XIV) ##STR30## is obtained, that isthen etherified according to processes known from theliterature(Houben-Weyl, "Methoden der Organ. Chemie", Vol. 6/3 I, p.49ff and 54ff) to (XI). The compound (XIII) can, in turn, be convertedusing known etherification reactions (literature reference see above)into (XII), before working continues for example as described with(XII). The compounds(XI) and (XIV) are valuable intermediate compoundsfor the synthesis of triazolinones and have hitherto not been describedin the literature and are therefore new.

The process claimed herein is suitable for the synthesis of bicyclictriazolines of formula (II) with the substitutions cited hereinabove aspreferred structures because these structures react particularly easilyand clearly or with particularly high yields according to the process toform triazolines. The course of the reaction for the preparation ofcompounds of general structure (II) is analogous to the preferredembodiment for the preparation of compounds of general formula (I). Theintermediate isolation of the corresponding intermediate compounds isnot necessary and without further working up the process can be carriedout in a reaction vessel without changing the solvent starting from (VI)and (XI) until the corresponding preferred compound of formula (II),toluene, acetonitrile, acetic acid ethyl ester, acetic acid methylester, acetic acid isopropyl ester methylene chloride and chloroformbeing suitable for this reaction. The reaction preferably occurs attemperatures between -20° C. and +70° C. The preferred bases used areorganic bases such as triethylamine, tributylamine, pyridine orinorganic bases such as Na₂ CO₃, K₂ CO₃, CaCO₃. Acids that arepreferably used are HCl, H₂ SO₄, H₃ PO₄, acetic acid, p-toluene sulfonicacid.

The process claimed is particularly preferred for the synthesis of 2-2,4-dichloro-5-(2-propynyloxy)phenyl!-5,6,7,8-tetrahydro-1,2,4-triazolo4,3-a!pyridine-3(2H)-one of formula IX) ##STR31## in which the compoundof formula (X) is obtained by ##STR32## reacting 2-piperidone with 2-6molar equivalents of phosgen or phosgen substitute in an inert organicsolvent, for example in an aromatic solvent such as toluene,chlorobenzene, a halogenated hydrocarbon such as chloroform, methylenechloride, an ether such as diisopropyl ether, tert. butylmethyl ether,tetrahydrofuran or diethylether, acetonitrile or carboxylic acid esters,for example acetic acid ethyl ester, acetic acid methyl ester or aceticacid isopropyl ester, at temperatures between -20° C. to 120° C.,preferably -20° C. to +70° C. in a manner known from the literatureaccording to U.S. Pat. No. 3,080,358 in over 94% yield. Excess phosgenis driven out and the solvent optionally withdrawn. At 0°-5° C. thecompound of formula (X) is added, optionally in the same solvent oranother above-cited solvent to a solution of the compound of formula(XI) or an acid addition salt of (XI), such as for example an HCL saltor an H₂ SO₄ salt ##STR33## in the same solvent or optionally in adifferent, above-cited solvent, optionally in the presence of an acidacceptor, for example of an organic base such as triethylaminetetramethyl piperidine, tributylamine or pyridine or of an inorganicbase such as NaOH, KOH, Ca(OH)₂, CaO, Na₂ CO₃, K₂ CO₃, CaCO₃, NaHCO₃,KHCO₃ or alcoholates such as NaOCH₃ or NaOC₂ H₅, where the compound(XVI) is first formed, ##STR34## which is then converted optionally inthe presence of an organic or inorganic acid such as for example HCl, H₂SO₄ HNO₃, HCO₂ H, p-toluene sulfonic acid, acetic acid, camphorsulfonicacid or H₃ PO₄ or of an acid ion exchanger and/or by increasing thetemperature, for example up to the boiling point of the solvent used,into the compound of formula (IX) ##STR35## The cyclisation from (XVI)to (IX) is advantageously carried out under acid catalysis and/ortemperature increase.

In the reaction to the compound (XVI) 1-4 molar equivalents of base arepreferably used, 1.5-3.5 molar equivalents being particularly preferred,where 1 molar equivalent of base serves to liberate the correspondingacylphenylhydrazine from the optionally used acylphenylhydrazine•acidaddition salt. A certain acid excess is needed to convert (cyclisation)compound (XVI) into (IX). It has been found that the reaction isaccelerated all the more, the greater the acid excess. The amount ofadded acid depends on the previously used amount of base. Particularlypreferred acids are H₂ SO₄ and HCl. Temperature increase, preferably upto the boiling point of the solvent, accelerates the cyclisation (IX).

In the process of the invention, skilful handling of the reaction doublyactivates 2 - piperidone in one step via the economically veryinteresting phosgenation or thiophosgenation, with the result that it ispossible to avoid a stepwise activation, such as for example accordingto EP 0 220 952, that is considerably more laborious from the point ofview of process technology and cost.

In the process according to the invention the reaction to (IX) alsooccurs starting from (X) and (XI) in one process step in the desiredmanner without need for intermediate working up. This means that,compared to known processes, such as described for example in DE 28 01429, a clear process technology advantage arises in that coupling,splitting off of the protecting group and cyclisation to the compound offormula (IX) can be achieved in only one step.

Using the procedure described, the reaction can occur starting from thecompounds (X) and (XI) in the single pot process and without isolationof intermediate steps, with the result that laborious working uptechniques are avoided and a smooth course of reaction is possible inthe process of the invention and the formation of by-products is largelyavoided and the total yield of (IX) increased. Similarly, the reactioncan occur with isolation of the intermediate step (XVI).

The invention will now be described with reference to the examples, butis not limited hereto.

EXAMPLES

Preparation of 2-2,4-dichloro-5-(2-propinyloxy)phenyl!-5,6,7,8-tetrahydro-1,2,4-triazolo4,3-a!pyridine-3(2H)-one and primary step sytheses

1) N-Chlorocarbonyl-2-chloro-1,4,5,6-tetrahydropyridine

Diphosgene (25 mmol=15,3 g) is prepared at -10° C. and active charcoal(0.25 g) added to accelerate the formation of phosgen. δ-Valerolactam(25 mmol=2.55 g) dissolved in acetic acid ethyl ester p.a. (20 ml) isadded dropwise in 1.5 hours at -10° to 0° C. The mixture is heated to25° C. until no more δ-valerolactam can be detected in the thin layerchromatogram. The mixture is heated slowly to 50° C., a strongdevelopment of gas being detectable. Only one product spot is visible inthe thin layer chromatogram. The active charcoal is filtered off and thefiltrate concentrated. 4.25 g (=94.4% yield) of the product is isolatedas a pale yellow oil.

2) Formic acid N'-(2,4-dichloro-5-hydroxyphenyl)-hydrazide sodium salt

2,4-Dichloro-5-hydroxyphenylhydrazine hydrochloride (11.5 g, 0.05 mol)is added to a solution of 30% methanolic solution of sodium methanolate(22.5 g, 0.125 mol) in methanol at room temperature. A suspension isformed to which methylformiate (62 ml, 1 mol) is added at the sametemperature. This mixture is then stirred for 2 hours at 40°-50° C. andthen over night at room temperature. The product is filtered off, thefilter residue is washed with methanol and the filtrate thenconcentrated under reduced pressure. The residue is taken up in tolueneand during concentration under reduced pressure a pale brown powder isformed that is combined with the above-mentioned filter residue. Yield:12.5 g (=99%) Melting point: 202°-204° C. (with decomposition)

3) Formic acid N'-(2,4-dichloro-5-(2-propinyloxy)-phenyl)hydrazide

A stirred suspension of formic acidN'-(2,4-dichloro-5-hydroxyphenyl)-hydrazide sodium salt (1.1 g, 5 mmol)in a mixture of 25 ml acetone and 25 ml water is reacted at roomtemperature with benzene sulfonic acid-(2-propargyl)ester (1.01 g, 5mmol). Sodium hydroxide solution (0,2 g, 5 mmol in 5 ml water) is addeddropwise within 30 minutes so that the pH value lies between 9.5 and 10.The result is reacted with 10 ml methanol to produce a clear solution.This is heated to 40° C. for 30 minutes during which a precipitateforms. The result is stirred over night, the product is filtered off andwashed with water. Yield: 0.8 g (61%) pale brown crystals Melting point:184° C.

4) 2-2,4-Dichloro-5-(2-propynyloxy)phenyl!-5,6,7,8-tetrahydro-1,2,4-triazolo4,3-a!pyridine-3(2H) -one

N-Chlorocarbonyl-2-chloro-1,4,5,6-tetrahydro-pyridine (4.32 g, 0.024mol) dissolved in 20 ml acetonitrile are added to a stirred suspensionof formic acid N'-(2,4-dichloro-5-(2-propinyloxy)-phenyl) hydrazide(5.18 g, 0.02 mol) in 250 ml acetonitrile at 0°-10° C. for 20 minutes.This is then reacted at the same temperature with triethylamine (4.04 g,0.04 mol) and dissolved in 20 ml acetonitrile. This is stirred for onehour at 5°-10° C. and a colourless precipitate precipitates out. This isheated for 4 hours to 50°-55° C. and then stirred for one night at roomtemperature. The batch is reacted with 30 ml 6N hydrochloric acid andstirred for 1 hour at 50° C. The solvent is drawn off under reducedpressure and the residue digested with iced water. The resultant palegrey precipitate is separated by filtration, washed with water and driedat 50°-60° C. Yield: 6.6 g (=97.6%) Melting point: 160°-162° C.

We claim:
 1. A process for the preparation of compounds of type (I),##STR36## wherein X=O or S,R¹ =(C₂ -C₈) alkoxyalkyl, (C₂ -C₈)haloalkoxyalkyl, (C₁ -C₈) alkyl, (C₁ -C₈) haloalkyl, (C₁ -C₈)cyanoalkyl, (C₂ -C₈) alkylthioalkyl, (C₂ -C₈) alkylsulfinylalkyl, (C₂-C₈) alkylsulfonylalkyl, (C₇ -C₈) arylalkyl, (C₂ -C₈) alkenyl, (C₂ -C₈)haloalkenyl, (C₂ -C₈) alkinyl, (C₂ -C₈) haloalkinyl, aryl, that may besubstituted one or more times with halogen, (C₁ -C₃) alkyl or (C₁ -C₃)alkoxy, heteroaryl, where heteroaryl may optionally be substituted byhalogen, R² and R³, independently of one another represent, H, (C₂ -C₆)alkoxyalkyl, (C₂ -C₆) haloalkoxyalkyl, (C₁ -C₆) alkyl, (C₁ -C₆)haloalkyl, (C₁ -C₆) cyanoalkyl, (C₁ -C₆) alkylthio, (C₂ -C₆)alkylthioalkyl, (C₂ -C₆) alkylsulfinylalkyl, (C₂ -C₆)alkylsulfonylalkyl, (C₇ -C₈) arylalkyl, (C₂ -C₆) alkenyl, (C₂ -C₆)haloalkenyl, (C₂ -C₆) alkinyl, (C₂ -C₆) haloalkinyl, aryl, that may besubstituted one or more times with halogen, (C₁ -C₃) alkyl or (C₁ -C₃)alkoxy, heteroaryl, where R¹ and R² may also be associated to form aring to produce structure (II), ##STR37## wherein n and m independentlyof one another are 0, 1, 2 or 3, Z=CR⁴ R⁵, O, S, S(O), S(O)₂, N((C₁-C₄)alkyl), N((C₁ -C₄)haloalkyl), C═O, C═N--R⁴ or C═S, R⁴ =H, (C₁ -C₃)alkyl, halogen, (C₁ -C₆) alkoxy, (C₁ -C₆) haloalkyl, (C₁ -C₆)haloalkoxy, (C₂ -C₆) alkylcarbonyloxy or (C₂ -C₆) haloalkylcarbonyloxy,R⁵ =H, (C₁ -C₃) alkyl or halogen, where R⁴ and R⁵, independently of oneanother, can substitute the ring one or more times and occupy up to 12(m=3, n=3) positions, Q stands for one of the radicals ##STR38## whereinW=O or S, R⁶ =H, halogen, R⁷ =H, (C₁ -C₈) alkyl, (C₁ -C₈) haloalkyl,halogen, OH, OR¹², SH, S(O)_(p) R¹², COR¹², CO₂ R¹², C(O)SR¹², C(O)NR¹⁴R¹⁵, CHO, CR¹⁴ ═NOR²¹, CHCR²² CO₂ R¹², CH₂ CHR²² CO₂ R¹², CO₂ N═CR¹⁶R¹⁷, NO₂, CN, NHSO₂ R¹⁸, NHSO₂ NHR¹⁸, NR¹² R²³, NH₂ or phenyl,optionally substituted by R²⁴, p=0,1 or 2, R⁸ =(C₁ -C₂) alkyl, (C₁ -C₂)haloalkyl, OCH₃, SCH₃, OCHF₂, halogen, CN or NO₂, R⁹ =H, (C₁ -C₃) alkylor halogen, R¹⁰ =H, (C₁ -C₃) alkyl, halogen, (C₁ -C₃) haloalkyl,cyclopropyl, Vinyl, (C₂ -C₈) alkinyl, CN, C(O)R²³,CO₂ R²³, C(O)NR²³ R²⁵,CR¹⁹ R²⁰ CN, CR¹⁹ R²⁰ C(O)R²³, CR¹⁹ R²⁰ CO₂ R²³, CR¹⁹ R²⁰ C(O)NR²³ R²⁵,CHR¹⁹ OH, CHR¹⁹ OC(O)R²³ or OCHR¹⁹ OC(O)NR²³ R²⁵, or, when Q equals Q-2,R⁹ and R¹⁰ can together with the carbon atom to which they are bound beC═O, R¹¹ =H, (C₁ -C₆) alkyl, (C₁ -C₆) haloalkyl, (C₃ -C₆) haloalkenyl,(C₂ -C₆) alkoxyalkyl, (C₃ -C₆) alkenyl, (C₃ -C₆) alkinyl, (C₃ -C₆)haloalkinyl, (C₄ -C₇) cycloalkylalkyl, ##STR39## R¹² =(C₁ -C₈) alkyl,(C₃ -C₈) cycloalkyl, (C₃ -C₈) alkenyl, (C₃ -C₈) alkinyl, (C₁ -C₈)haloalkyl, (C₂ -C₈) alkoxyalkyl, (C₂ -C₈) alkylthioalkyl, (C₂ -C₈)alkylsulfinylalkyl, (C₂ -C₈) alkylsulfonylalkyl, (C₄ -C₈)alkoxyalkoxyalkyl, (C₄ -C₈) cycloalkylalkyl, (C₆ -C₈) cycloalkoxyalkyl,(C₄ -C₈) alkenyloxyalkyl, (C₄ -C₈) alkinyloxyalkyl, (C₃ -C₈)haloalkoxyalkyl, (C₄ -C₈) haloalkenyloxyalkyl, (C₄ -C₈)haloalkinyloxyalkyl, (C₆ -C₈) cycloalkylthioalkyl, (C₄ -C₈)alkenylthioalkyl, (C₄ -C₈) alkinylthioalkyl, (C₁ -C₄) alkyl, substitutedby phenoxy or benzyloxy, each ring optionally substituted by halogen,(C₁ -C₃) alkyl or (C₁ -C₃) haloalkyl, (C₄ -C₈) trialkylsilylalkyl, (C₃-C₈) cyanoalkyl, (C₃ -C₈) halocycloalkyl, (C₃ -C₈) haloalkenyl, (C₅ -C₈)alkoxyalkenyl, (C₅ -C₈) haloalkoxyalkenyl, (C₅ -C₈) alkylthioalkenyl,(C₃ -C₈) haloalkinyl, (C₅ -C₈) alkoxyalkinyl, (C₅ -C₈)haloalkoxyalkinyl, (C₅ -C₈) alkylthioalkinyl, (C₂ -C₈) alkylcarbonyl,benzyl, optionally substituted by halogen, (C₁ -C₃) alkyl or (C₁ -C₃)haloalkyl, CHR¹⁹ COR¹³, CHR¹⁹ P(O)(OR¹³)₂, CHR¹⁹ P(S)(OR¹³)₂,P(O)(OR¹³)₂, P(S) (OR¹³)₂, CHR¹⁹ C(O)NR¹⁴ R¹⁵, CHR¹⁹ C(O)NH₂, CHR¹⁹ CO₂R¹³, CO₂ R¹³, SO₂ R¹³, phenyl, optionally substituted by R²⁴, ##STR40##R¹³ =(C₁ -C₆) alkyl, (C₁ -C₆) haloalkyl, (C₃ -C₆) alkenyl or (C₃ -C₆)alkinyl, R¹⁴ and R¹⁶ =independently of one another, H or (C₁ -C₄) alkyl,R¹⁵ and R¹⁷ =independently of one another, (C₁ -C₄) alkyl or phenyl,optionally substituted by halogen, (C₁ -C₃) alkyl or (C₁ -C₃) haloalkyl,or R¹⁴ and R¹⁵ can, together with the nitrogen atom that binds them,form a piperidinyl-, pyrrolidinyl- or morpholinyl-ring, each ringoptionally substituted by (C₁ -C₃) alkyl, phenyl or benzyl, or R¹⁶ andR¹⁷ can, together with the carbon atom that binds them, be (C₃ -C₈)cycloalkyl, R¹⁸ =(C₁ -C₄) alkyl or (C₁ -C₄) haloalkyl, R¹⁹ and R²⁰=independently H or (C₁ -C₅) alkyl, R²¹ =H, (C₁ -C₆) alkyl, (C₃ -C₆)alkenyl or (C₃ -C₆) alkinyl, R²² and R²⁷ =independently of one another,H, (C₁ -C₄) alkyl or halogen, or R¹² and R²² can together form a (C₂-C₃) alkylen, R²³, R²⁴ and R²⁸ =independently of one another, H or (C₁-C₄) alkyl, R²⁵ =(C₁ -C₂) alkyl, (C₁ -C₂) haloalkyl, OCH₃, SCH₃, OCHF₂,halogen, CN or NO₂ and R²⁶ =H, (C₁ -C₅) alkyl, (C_(1-C) ₅) haloalkyl,(C₃ -C₆) cycloalkyl, (C₃ -C₆) halocycloalkyl, (C₁ -C₅) alkoxy, (C_(1-C)₅) haloalkoxy and phenyl, that may optionally be substituted up to threetimes optionally by halogen, NO₂, cyano, (C₁ -C₂) alkyl, (C₁ -C₂)haloalkyl, (C₁ -C₂) alkoxy or (C₁ -C₂) haloalkoxy, R²⁹ =H, halogen or(C₁ -C₆) alkyl, R³⁰ =H, (C₁ -C₄) alkyl or halogen, wherein amides offormula (IV) ##STR41## wherein R¹, R² and R³ have the meaning givenabove are reacted with phosgen or thiophosgen or a phosgen substitute orthiophosgen substitute optionally in a solvent to a compound of formula(V) ##STR42## wherein R¹, R² and R³ and X have the meaning given aboveand these compounds of formula (V) are then reacted with a compound offormula (VI) or an acid addition salt thereof,

    Q--NH--NH--CO--R.sup.26                                    (VI)

wherein Q and R² ²⁶ have the meaning given above optionally in thepresence of a diluting agent and optionally initially in the presence ofa base and then in the presence of an acid and optionally by increasingthe temperature to a compound of formulae (I) or (II).
 2. The process ofclaim 1, wherein the synthesis sequences occur in a reaction vesselstarting from the compounds of formulae (X) and (XI) withoutintermediate isolation.
 3. The process of claim 1, wherein the citedsynthesis sequence occurs without changing the solvent.
 4. The processof claim 1, wherein organic or inorganic acids selected from HCl, H₂SO₄, HNO₃, HCO₂ H, p-toluene sulfonic acid, acetic acid, camphorsulfonicacid or H₃ PO₄ or an acid ion exchanger are used as the acid.
 5. Theprocess of claim 4, wherein hydrochloric acid, sulfuric acid orphosphoric acid is used as the acid.
 6. The process of claim 1, whereinthe reaction sequence is carried out at a temperature between -20° C.and 120° C.
 7. The process of claim 1, wherein acetic acid ethyl esteror acetonitrile or mixtures of the two are used as the solvent.
 8. Theprocess of claim 1, wherein an organic base, an inorganic base or analcoholate is used as the base.
 9. The process of claim 8, whereintriethylamine, tributylamine, pyridine, tetramethylpiperidine, NaOH,KOH, Ca(OH)₂, Na₂ CO₃, K₂ CO₃, CaCO₃, NaHCO₃, KHCO₃, NaOCH₃ or NaOC₂ H₅is used as the base.
 10. The process of claim 9, wherein K₂ CO₃, Na₂CO₃, triethylamine or tributylamine is used as the base.
 11. A processof claim 1, wherein the reaction sequence is carried out at atemperature between -20° C. and 80° C.
 12. The process of claim 1,wherein R¹ is a benzyl.
 13. The process of claim 1, wherein R¹ is anaphthyl or phenyl.
 14. The process of claim 1, wherein R¹ is apyridine.
 15. The process of claim 1, wherein R² and/or R³ are a benzyl.16. The process of claim 1, wherein R² and/or R³ are a naphthyl orphenyl.
 17. The process of claim 1, wherein R² and/or R³ are a pyridine.